Coherent Stokes and anti-Stokes Raman spectra of the ν1 (A1) and ν2 (E) bands of SF6 and UF6

Coherent Stokes and anti-Stokes Raman scattering are used to study the ν₁ and ν₂ spectral band profiles of UF₆ and SF₆. Most of the observed SF₆ “hot” bands are assigned, leading to evaluations of the anharmonicity constants X_ij: X₁₂ = ?(2.80 ± 0.30) cm^?1, X₁₄ = ?(1.00 ± 0.15) cm^?1, X₁₅ = ?(1.00 ± 0.15) cm^?1. For UF₆, a tentative assignment of the “hot” bands is made: X₁₂ = ?(1.80 ± 0.30) cm^?1, X₁₃ = ?(1.60 ± 0.30) cm^?1, X₁₄ = ?(0.20 ± 0.10) cm^?1, X₁₅ = ?(0.25 ± 0.10) cm^?1, and X₁₆ = ?(0.10 ± 0.05) cm^?1. Parameters such as the vibration-rotation coupling constants are determined. For SF₆: α = (7 ± 2) × 10^?5 cm^?1 for the ν₂ band and α = ?(1.02 ± 0.01) 10^?4 cm^?1 for the ν₁ band. The calculated spectral profiles of the coherent Stokes or anti-Stokes spectra, which are in good agreement with experimental results, give values for the resonant and nonresonant parts of the susceptibility in both molecules. They also show, in some cases, the influence of neighboring combination bands.     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

The ν4 and ν2 Raman bands of CHD3

The CHD₃ Raman spectrum from 1925 to 2455 cm^?1 has been photographed with a resolution of about 0.2 cm^?1, showing the overlapping ν₂ and ν₄ bands. Ground state combination differences yield C₀ = 2.6297 ± 0.0003 cm^?1. The ν₄ state is weakly perturbed, but reasonably accurate values could be obtained for ν₄ = 2250.88 ± 0.10 cm^?1, (Cζ)₄ = 0.656 ± 0.010 cm^?1, C₄ - C₀ and B₄ - B₀. Some of these constants differ significantly from values previously estimated by infrared workers. For the ν₂ state the constants determined are in good agreement with recent infrared results.     

Li ion conduction in Li2ZrO3, Li4ZrO4, and LiScO2

The results of ac and dc conductivity measurements on Li₂ZrO₃, Li₄ZrO₄, and LiScO₂ show that these phases are Li ion conductors. Even though the Li ion conductivity in these phases is quite low, 3.3×10^?5, 3.0×10^?4, and 4.2×10^?7 S m^?1 at 573 K, respectively, they are of special interest since they are among the small group of ternary oxides which may be thermodynamically stable against Li. Mechanisms are proposed for the decomposition of these phases at the anode due to Li loss during dc polarization. In addition the electrical conductivity of ternary oxide phases which are, or may be, thermodynamically stable against Li are summarized.     

Continuous-wave CO2 laser spectroscopy of SF6, WF6, and UF6

The linear absorption of CO₂ laser radiation in SF₆, WF₆, and UF₆ has been measured by using optoacoustic detection techniques. Absolute absorption coefficients per Torr as low as 1 × 10^?7 cm^?1 Torr^?1 in a 2-cm active path length could be measured by taking advantage of calibration measurements performed with SF₆.     

Fourier transform spectroscopy on the 3ν2, 2ν2 + ν6 and ν3 + ν5 bands of H2CO

Fourier transform spectra covering the range from 1500 to 5400 cm^?1 with 0.02-cm^?1 resolution have been obtained for formaldehyde. A study of the region above 4000 cm^?1 has yielded rotational constants and other asymmetric rotor parameters for three bands: 3ν₂ (ν₀ = 5177.7611 ± 0.0005 cm^?1)2ν₂ + ν₆ (ν₀ = 4734.193 ± 0.004 cm^?1), and ν₃ + ν₅ (ν₀ = 4335.102 ± 0.001 cm^?1). An analysis of the A-type Coriolis interaction between the 2ν₂ + ν₆ state and the unobserved 2ν₂ + ν₄ state has yielded partially deperturbed rotational constants for the 2ν₂ + ν₆ state. Vibration-rotation interaction constants have been obtained for the ν₂ and ν₆ normal modes by combining the present results with those of previous workers.     

Absorption spectra of C6H6 and C6D6 near 340 nm

The absorption spectra of C₆H₆ and C₆D₆ in the liquid phase have been studied near 340 nm. The absorption spectrophotometric mounting was a sequential double-beam attachment with linear response to energy on scanning of the spectrum before the exit slit and an electronic device which gives directly either the absorbance or the integrated absorbance of a transition and, consequently, its oscillator strength.The oscillator strength measured for the band of C₆H₆ is 8×10^?8, which corresponds to a dipole moment of 2.4×10^?3 Debye; this value is of the same order as a theoretical value calculated by Tsubomura and Mulliken (3.8×10^?3 Debye) for a transition between states ³F and ³A of an oxygen-benzene pair. This agreement corroborates the hypothetical existence of such a transition.The first vibrational band is at 28553 cm^?1 for C₆H₆; this band is not observed in the vapor or solid phase. It corresponds probably to the transition 0-0, which is considered in the literature to be near 29500 cm^?1. The isotopic shift measured for this first band is 164 cm^?1. The vibrational frequencies are, respectively, 910 cm^?1 for C₆H₆ and 889 cm^?1 for C₆D₆.     

Tunable laser study of the ν10 + ν11 band of cyclopropane

Diode laser measurements of the ν₁₀ + ν₁₁ (l_tot = ±2) perpendicular band of cyclopropane have led to the assignments of roughly 600 lines in the 1880–1920-cm^?1 region. Most of the spectra were recorded and stored in digital form using a rapid-scan mode of operating the laser. These spectra were calibrated, with the aid of a computer, by reference to the R lines of the ν₁ + ν₂ band of N₂O. The ground state constants we obtained are (in cm^?1) B = 0.670240 ± 2.4 × 10^?5, D_J = (1.090 ± 0.054) × 10^?6, D_JK = (?1.29 ± 0.19) × 10^?6, D_K = (0.2 ± 1.1) × 10^?6. The excited state levels are perturbed at large J values, presumably by Coriolis couplings between the active E′(l_tot = ±2) and the inactive A′(l_tot = 0) states. Effective values for the excited state constants were obtained by considering only the J < 15 levels. The A₁-A₂ splittings in the K′ = 1 excited states were observed to vary as q_effJ(J + 1), with q_eff = (2.17 ± 0.17) × 10^?4 cm^?1.     

High-resolution infrared spectrum of the ν2 + ν3 band of 14N16O2

The ν₂ + ν₃ band of ¹⁴N¹⁶O₂ has been recorded with resolution of 0.028 cm^?1. Ground state and upper state rotational constants have been obtained. The band center obtained, ν₀ = 2355.1517 ± 0.0011 cm^?1 (error cited is 3σ), has been combined with the band centers recently determined for ν₃ and ν₂ to calculate X₂₃ = ?11.348 ± 0.020 cm^?1 where the uncertainty cited is based on reasonable estimates of the absolute frequency error.     

Phonon coupled cooperative low-spin 1A1high-spin 5T2 transition in [Fe(phen)2(NCS)2] and [Fe(phen)2(NCSe)2] crystals

Heat capacities of [Fe(phen)₂(NCS)₂] and [Fe(phen)₂(NCSe)₂] were measured between 13⁵ and 375 K. A heat capacity anomaly due to the spin-transition from low-spin ¹A₁ to high-spin π₂ electronic ground state was found at 176·29 K for the SCN-compound and at 231·26 K for the SeCN-compound, respectively. Enthalpy and entropy of transition were determined to be ΔH = 8·60 ± 0·14 kJ mol^?1 and ΔS = 48·78 ± 0·71 J K^?1 mol^?1 for the SCN-compound and ΔH = 11·60 ± 0·44 kJ mol^?1 and ΔS = 51·22 ± 2·33 J K^?1 mol^?1 for the SeCN-compound. To account for much larger value of ΔS compared with the magnetic contribution, we suggest that there is significant coupling between electronic state and phonon system. We also present a phenomenological theory based on heterophase fluctuation. Gross aspects of magnetic, spectroscopic, and thermal behaviors were satisfactorily accounted for by this model. To examine closely the transition process, infrared spectra were recorded as a function of temperature in the range 4000 ? 30 cm^?1. The spectra revealed clearly the coexistence of the ¹A₁, and the ⁵T₂ ground states around T_c.     

Determination of A0 for CH335Cl and CH337Cl from the ν4 infrared and Raman bands

The ν₄ infrared and Raman bands of CH₃Cl were analyzed simultaneously. A direct fit yielded a complete set of constants for CH₃³⁵Cl, including A₀ = 5.20530 ± 0.00010 cm^?1 and D_K = (8.85 ± 0.13) × 10^?5cm^?1. For CH₃³⁷Cl an incomplete set of constants was obtained from the infrared band, and A₀ = 5.2182 ± 0.0010 cm^?1 was estimated by curve fitting of the Raman spectrum. The resulting equilibrium structure is $\text{r(}\text{CH) = 1.0854 ± 0.0005}\text{A}\text{?}$, $\text{r(}\text{CCl) = 1.7760 ± 0.0003}\text{A}\text{?}$, and <(HCH) = 110°.35 ± 0°.05.     

Spectral intensities in the ν3 bands of 12CH4 and 13CH4

Relative and absolute line intensities for the ν₃ bands of the ¹²C and ¹³C isotopic varieties of methane have been measured using a tunable difference-frequency laser spectrometer. From these data the integrated band strength of ¹³CH₄ is calculated to be 0.983 ± 0.007 that of ¹²CH₄, with the uncertainty representing three standard deviations. The absolute ν₃ bandstrength for ¹²CH₄ is 266.1 ± 3.0 cm^?2 atm ^?1 at 294.7 K where the errors are dominated by the pressure measurement. This band strength corresponds to an effective transition moment 〈μ₃〉 = 0.0534(3)D for ¹²CH₄ from which the ν₄ band dipole moment and the Herman-Wallis F factor can be estimated using a recent force field model for methane.     

The bending vibration bands ν4 and ν5 of HCCI

The bending vibration bands ν₄ and ν₅ of HCCI were studied. From the observed rotational structure the rotational constant B₀ and the centrifugal distortion constant D₀ were obtained. The results were B₀ = 0.105968(7) cm^?1 and D₀ = 1.96(7) × 10^?8 cm^?1 from ν₄ and B₀ = 0.105948(8) cm^?1 and D₀ = 1.96(11) × 10^?8 cm^?1 from ν₅. The structure of the hot bands 2ν₅(Δ) ← ν₅(Π) and 3ν₅(φ) ← 2ν₅(Δ) was also resolved and hence the values α₅ = ?3.033(8) × 10^?4 cm^?1 and q₅ = 9.3(3) × 10^?5 cm^?1 could be derived. The other most intense hot bands following ν₅ could be explained in terms of the Fermi diads $\text{ν}{}_3\text{2ν}{}_5{}^0$ and $\text{ν}{}_3\text{+}\text{ν}{}_5{}^{\mathrm{\pm 1}}\text{3ν}{}_5{}^{\mathrm{\pm 1}}$. Of the numerous hot bands accompanying ν₄, only those between different excited states of ν₄ could be assigned. Then estimates for α₄ and q₄ were also obtained. In addition, several vibrational constants were derived.     

Absolute intensity measurements of the CO2 bands 401III←000 and 411III←010

The absolute intensities of the transitions 401_III←000 and 411_III←010 of CO₂ have been measured from spectra obtained under high resolution. Both the vibration-rotation line intensities and the integrated band intensities are reported. The rotationless transition moment of 401_III←000 is deduced and a vibration-rotation interaction factor F(m) = 1+(4.92×10^?4)m+(4.4×10^?7)m² is determined. The values obtained are: S_Band(401_III←000) = (25.54±0.22)×10^?5 cm^?2atm_{(293 K)}^?1, |R₀₀₀^401_III| = (1.87±0.02)×10^?4D, and S_Band(411_III←010) = (1.83±0.13)×10^?5 cm^?2atm_{(293 K)}^?1.     

Diode laser measurements of the band strengths of ν3 and ν6 in 12CH3D

A diode laser spectrometer has been used to measure line strengths for 143 transitions in the ν₆ fundamental band of ¹²CH₃D near 9 μm. These line-strength measurements have been used to derive a band strength for ν₆ and ν₃. The band strength derived for ν₆ is 61.7 ± 1.8 cm^?2 atm^?1, and that for ν₃ is 49.3 ± 1.4 cm^?2 atm^?1 at 395 K.     

Ferroelectric and optical properties of Ba6Ti2Nb8O30 single crystals

The dielectric, optical and non-linear optical properties of Ba₆Ti₂Nb₈O₃₀ single crystals were examined from room temperature up to the Curie temperature of 245°C. The spontaneous polarization at room temperature was estimated as 0·22±0·01 C/m². The linear electrooptic constants were measured as r₃₃^T=(1·17±0·02)×10^?10 and r₁₃^T=(0·42±0·01)×10^?10 m/V. The non-linear optical coefficients were d₃₃=(15·1±2·0)×10^?12 and d₃₁=(11·0±2·0)×10^?12 m/V, which are comparable to those of Ba₄Na₂Nb₁₀O₃₀. Temperature dependences of δ₃₃ and δ₃₁ (Miller's δ) were found to be proportional to that of P_s.     

Study of the ν2 + ν3 and 2ν6 infrared bands of CH379Br and CH381Br

The rotational analysis of the ν₂ + ν₃ band, centered around 1912 cm^?1, and of both components 2ν₆^±2 and 2ν₆⁰, centered about 1912 and 1904 cm^?1, respectively, has been carried out from a Fourier transform spectrum having a resolution limit of 0.005 cm^?1. A standard deviation of about 0.001 cm^?1 was obtained for about 750 lines of the unperturbed 2ν₆^±2 component for both isotopic species. The ν₂ + ν₃ band, stronger than 2ν₆^±2, is perturbed by two resonances: a Coriolis resonance with the very weak ν₃ + ν₅ band, no line of which has been observed, and an anharmonic resonance with 2ν₆⁰, only four K subbands of which have been observed. For both isotopic species, a standard deviation of about 0.002 cm^?1 has been obtained for about 750 lines of ν₂ + ν₃ and 2ν₆⁰.     

High-resolution infrared spectrum of the ν2 and ν8 bands of CH2D2

A high-resolution infrared spectrum of methane-d₂ has been measured in the C-D stretching band region (2025–2435 cm^?1). Rotational structures of the ν₂ and ν₈ bands have been assigned by use of the ASSIGN-diagram method, and the c-type Coriolis interaction between ν₂ and ν₈ has been analyzed. The band origins, ν₂ = 2203.22 ± 0.01 cm^?1 and ν₈ = 2234.70 ± 0.01 cm^?1, the rotational constants and the centrifugal distortion constants for the two bands, and the Coriolis coupling constant, $\text{∥;ξ}{}_{28}{}^{\mathrm{c}}\text{∥; = 0.182 ± 0.015}\text{cm}{}^{\mathrm{?1}}$, have been determined.     

克里奇中间体CH2OO与CF3CF=CF2反应的动力学研究

本文使用OH激光诱导荧光方法研究了结构最简单的克里奇中间体CH₂OO和CF₃CF=CF₂的反应动力学. 在压强为10 Torr条件下,测量了温度在283,298,308和318 K的反应速率常数,分别为(1.45±0.14)×10^-13,(1.18±0.11)×10^-13,(1.11±0.08)×10^-13和(1.04±0.08)×10^-13 cm³·molecule^-1·s^-1. 根据阿伦尼乌斯方程,获得该反应的活化能为(-1.66±0.21) kcal/mol. 在6.3∽70 torr压力范围内,未观察到该反应的速率常数存在压力相关.     

The high-resolution infrared spectrum of the ν11 band of allene-d4

The infrared band ν₁₁ around 300 cm^?1 of allene-d₄ has been studied at a resolution of 0.010 cm^?1. The J structure in the central Q branches of this perpendicular band was resolved and P- and R-lines were assigned to subbands with {K″} ≦ 18. A ground-state analysis resulted in B₀ = 0.232187(30) cm^?1, D₀^J = 6.3(1.0) × 10^?8cm^?1, and D₀^JK = 3.0(4) × 10^?6cm^?1. Upper-state constants including η₁₁^J and η₁₁^K were derived. Special attention was paid to the study of l-type doublings. Doublets due to q^(?)-doubling were resolved and accordingly the value q₁₁^(?) = ?0.000160(3) cm^?1 was derived. The more usual q⁽⁺⁾-doubling was also observed, and the result q₁₁⁽⁺⁾ = 0.000144(4) cm^?1 was obtained.